Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
  • B01J31/124—Silicones or siloxanes or comprising such units
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/48—Silver or gold
  • B01J23/52—Gold
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/44—Palladium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the invention generally relates to an improved catalytic process for decomposing alkyl or aromatic hydroperoxides to form a mixture containing the corresponding alcohol and ketone.
• the invention relates to decomposing a hydroperoxide by contacting it with a catalytic amount of a heterogeneous Au catalyst that has been treated with an organosilicon reagent.
• K/A ketone/alcohol
• adipic acid or caprolactam which are important reactants in processes for preparing certain condensation polymers, notably polyamides.
• a high K/A ratio in the reaction mixture is generally preferred. Due to the large volumes of adipic acid consumed in these and other processes, improvements in processes for producing adipic acid and its precursors can be used to provide beneficial cost advantages.
• Druliner et al. (WO 98/34894) used a heterogeneous gold catalyst in an improved catalytic process for decomposing alkyl or aromatic hydroperoxides to form a mixture containing the corresponding alcohol and ketone.
• Organosilicon compounds have for some time been employed in the treatment of inorganic oxide surfaces such as inorganic oxide films, particulates and pigments, and fibers (such as glass fibers, aluminum fibers and steel fibers).
• the typical organosilicon treatment involves coating such surfaces with a hydrolyzate (and/or condensate of the hydrolyzate) of an organofunctional hydrolyzable silane.
• the treatment is typically supplied to the surface of the inorganic oxide whereby through the hydrolyzable groups or silanol groups ( ⁇ Si—OH), bonding through siloxy moieties ( ⁇ Si—O—) is effected.
• U.S. Pat. No. 4,451,572 describes a surface modified zeolite produced by reacting the zeolite with an organosilane.
• WO 99/02264 describes but does not exemplify a supported ultrafine gold particle catalyst that has been rendered hydrophobic for the synthesis of hydrogen peroxide, one method of which is by treatment with silane.
• Disclosed herein is an improved process for decomposing a hydroperoxide to form a decomposition reaction mixture containing a corresponding alcohol and ketone, the improvement comprising decomposing the hydroperoxide by contacting the hydroperoxide with a catalytic amount of a heterogeneous gold catalyst wherein the gold catalyst has been silanized with an organosilicon reagent. Further disclosed is the process wherein the heterogenous catalyst is supported on a catalyst support member.
• the present invention provides an improved process for conducting a hydroperoxide decomposition step in an industrial process in which an alkyl or aromatic compound is oxidized to form a mixture of the corresponding alcohol and ketone.
• cyclohexane can be oxidized to form a mixture containing cyclohexanol (A) and cyclohexanone (K).
• the industrial process involves two steps: first, cyclohexane is oxidized, forming a reaction mixture containing CHHP; second, CHHP is decomposed, forming a mixture containing K and A.
• processes for the oxidation of cyclohexane are well known in the literature and available to those skilled in the art.
• the improved process can also be used for the decomposition of other alkane or aromatic hydroperoxides, for example, t-butyl hydroperoxide, cyclododecylhydroperoxide and cumene hydroperoxide.
• heterogeneous catalytic process relative to processes employing homogenous metal catalysts, such as metal salts or metal/ligand mixtures, include longer catalyst life, improved yields of useful products, and the absence of soluble metal compounds.
• heterogeneous catalysts subject the process to fouling by water and organic impurities from the oxidation reaction, especially acidic impurities. Removal of these impurities prevents fouling of the catalyst, which thereby extends the catalyst lifetime.
• the heterogeneous catalysts of the invention comprise Au and Au compounds, preferably applied to suitable solid supports, that have been silanized by an organosilicon reagent.
• the catalysts after treatment are extremely hydrophobic while showing no decrease in activity as compared to the untreated catalyst.
• the inventive process may also be performed using Au in the presence of other metals, preferably metals of Periodic Group VIII, more preferably Pd.
• the metal to support percentage can vary from about 0.01 to about 50 percent by weight, and is preferably about 0.1 to about 10 wt. percent.
• Suitable and presently preferred supports include SiO 2 (silica), Al 2 O 3 (alumina), C (carbon), TiO 2 (titania), MgO (magnesia) or ZrO 2 (zirconia).
• Alumina is a particularly preferred support, and Au supported on alumina is a particularly preferred catalyst of the invention.
• a preferred catalyst is 0.1-10% Au/0.05-2% Pd on ⁇ -alumina, more preferably 1% Au/0.1% Pd on ⁇ -alumina.
• heterogeneous catalysts of the invention can be obtained already prepared from manufacturers, or they can be prepared from suitable starting materials using methods known in the art.
• Supported gold catalysts can be prepared by any standard procedure known to give well-dispersed gold, such as sol-gel techniques, evaporative techniques or coatings from colloidal dispersions.
• ultra-fine particle sized gold is preferred.
• small particulate gold (often smaller than 10 nm) can be prepared according to Haruta, M., “Size-and Support-Dependency in the Catalysis of Gold”, Catalysis Today 36 (1997) 153-166 and Tsubota et al., Preparation of Catalysts V, pp. 695-704 (1991).
• Such gold preparations produce samples that are purple-pink in color instead of the typical bronze color associated with gold and result in highly dispersed gold catalysts when placed on a suitable support member.
• These highly dispersed gold particles typically are from about 3 nm to about 25 nm in diameter.
• the catalyst solid support including SiO 2 , Al 2 O 3 , carbon, MgO, zirconia, or TiO 2 , can be amorphous or crystalline, or a mixture of amorphous and crystalline forms. Selection of an optimal average particle size for the catalyst supports will depend upon such process parameters as reactor residence time and desired reactor flow rates. Generally, the average particle size selected will vary from about 0.005 mm to about 5 mm. Catalysts having a surface area larger than 10 m 2 /g are preferred since increased surface area of the catalyst has a direct correlation with increased decomposition rates in batch experiments.
• a preferred support is alumina; more preferred is ⁇ -alumina and ⁇ -alumina.
• Adding air or a mixture of air and inert gases to CHHP decomposition mixtures provides higher conversions of process reactants to K and A, since some cyclohexane is oxidized directly to K and A, in addition to K and A being formed by CHHP decomposition.
• This ancillary process is known as “cyclohexane participation”, and is described in detail in Druliner et al., U.S. Pat. No. 4,326,084, the entire contents of which are incorporated by reference herein.
• Other gases may also be added or co-fed to the reaction mixture as needed. Inert gases such as nitrogen may also be added to the reaction alone or in combination with other gases.
• the results of the CHHP decomposition reaction can be adjusted by choice of catalyst support, gases added to the reaction mixture, or metals added to the the heterogenous catalysts of the invention.
• metals added to the heterogenous catalysts of the invention are for use as promoters, synergist additives, or co-catalysts are selected from Periodic Group VIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt. Most preferred is Pd and Pt.
• One preferred gas that can be added to the reaction mixture is hydrogen.
• An advantage of the addition of hydrogen is that the K/A ratio can be varied according to need.
• the addition of hydrogen can also convert impurities or by-products of the reactions, such as benzene, to more desirable products.
• the catalysts can be contacted with CHHP by formulation into a catalyst bed, which is arranged to provide intimate contact between catalysts and reactants.
• catalysts can be slurried with reaction mixtures using techniques known in the art.
• the process of the invention is suitable for batch or for continuous CHHP decomposition processes. These processes can be performed under a wide variety of conditions.
• Silanized is defined herein to refer to treatment of the catalyst with either at least one silane, or a mixture of at least one silane and at least one polysiloxane (collectively referred to herein as organosilicon compounds).
• Suitable silanes have the formula R x Si(R′) 4-x wherein R is a nonhydrolyzable aliphatic, cycloaliphatic or aromatic group having at least 8 to about 20 carbon atoms;
• silanes useful in carrying out the invention include octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadercyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane and octadecyltriethoxysilane.
• Weight content of the silane, based on total silanized catalyst is typically about 0.05 to about 3 weight %, preferably about 0.1 to about 2 weight %.
• a mixture of at least one silane with at least one polysiloxane is useful in carrying out the invention.
• Suitable polysiloxanes have the formula: ( R n ⁇ SiO 4 - n 2 ) m
• polydimethylsiloxane PDMS
• vinyl phenylmethyl terminated dimethyl siloxanes vinyl phenylmethyl terminated polydimethyl siloxane and the like are suitable polysiloxanes.
• PDMS is a preferred polysiloxane.
• Weight content of the silane and polysiloxane is about 0.1 to about 5.0 weight %, preferably from about 0.2 to 3 weight %.
• the ratio of silane to polysiloxane can be 1 silane:2 polysiloxane up to 2 silane:1 polysiloxane.
• the silanes and polysiloxanes are commercially available or can be prepared by processes known in the art such as those described in “Organosilicon Compounds”, S. Pawlenko, et al., New York (1980).
• the method of addition is not especially critical and the catalyst may be treated with the silane in a number of ways.
• the silane addition can be made neat or prehydrolyzed to a dry base, from a slurry, a filtration step, during drying or at a size operation such as a fluid energy mill, e.g., micronizer, or media mill as described in greater detail in Niedenzu, et al, U.S. Pat. No. 5,501,732, or post blending after micronizing.
• the polysiloxane addition can be made in conjunction with the silane or post addition to the silanized support.
• An alternate embodiment that is contemplated is the use of other members of Periodic Groups IV and V in place of Si, such as Ge, P, and As.
• the catalysts of the invention would thereby be treated with compounds that are the equivalent of the silanes of the instant invention, such as R x Ge(R′) 4-x , R x P(R′) 3-x ⁇ , etc.
• Examples 1-7 (Table I) vials were analyzed directly for the amount of CHHP remaining, using a 15 m DB-17 capillary column with a 0.32 mm internal diameter.
• the liquid phase of the column was comprised of (50 wt % phenyl) methyl polysiloxane.
• the column was obtained from J. and W. Scientific, Folsum, Va.
• R.F. CHHP GC response factor for CHHP
• Stock solutions consisted of mixtures of about 20 wt % CB in CHHP.
• the CHHP source contained up to 2.0 wt % of combined cyclohexanol and cyclohexanone. Vials were removed from the aluminum heater/stirrer after a 4 or 8 minute period and were allowed to cool to ambient temperature. Results indicate that the silane reagent does not significantly reduce the catalytic activity of the gold catalysts.

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• 2000
  • 2000-08-18 EP EP00955769A patent/EP1309534B1/fr not_active Expired - Lifetime
  • 2000-08-18 WO PCT/US2000/022867 patent/WO2002016296A1/fr active IP Right Grant
  • 2000-08-18 KR KR10-2003-7002297A patent/KR20030034145A/ko not_active Application Discontinuation
  • 2000-08-18 DE DE60023358T patent/DE60023358T2/de not_active Expired - Lifetime
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